Oilfield cleaner and corrosion inhibitor comprising a polyamine sulfonic acid salt

ABSTRACT

Disclosed herein are cleaner/corrosion inhibiting compositions useful in applications relating to the production, transportation, storage, and separation of crude oil and natural gas. Also disclosed herein are methods of using the compositions as cleaners/corrosion inhibitors, particularly in applications relating to the production, transportation, storage, and separation of crude oil and natural gas.

CROSS-REFERENCED TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/842,194, filed Jul. 2, 2013, the entirety ofwhich is herein incorporated by reference.

FIELD OF THE INVENTION

The present disclosure relates generally to cleaner/corrosion inhibitorcompositions, and more particularly to compositions for removingoilfield hydrocarbon and iron sulfide based deposits from equipment andfor providing protection to the equipment against corrosive fluids andgases.

BACKGROUND OF THE INVENTION

As oilfields age, the amount of oil produced decreases and the amount ofwater produced with the oil, increases. This water is usually disposedof or injected back into the formation to maintain reservoir pressure.The separation process is efficient, but not perfect, and a smallfraction of oil and other debris can be present after the fluids passthrough the separation equipment. That residual fraction of oil in watercarryover can cause significant problems as the field ages. Fields canproduce as much as 1,000,000 barrels of water each day. The residual oiland other particles such as paraffin, asphaltenes, iron sulfide andbiomass can build up in the separation equipment and pipelines. Thisform of deposit is referred to in the industry as schmoo. If leftuntreated, this form of deposition can plug lines, which can lead toloss of revenue and/or equipment failure, and further, can result incasualties. Due to lines which cannot be mechanically cleaned, achemical solution is needed that can be injected into the system tomaintain control of the deposition in the lines.

Fluids produced in the oil and gas industry can be quite corrosive tothe infrastructure by which it is produced. This internal corrosion ofpipelines and production equipment is commonly treated using chemicalcorrosion inhibitors. Corrosion inhibitors work primarily by formingprotective films on the surfaces of the infrastructure. This creates aprotective barrier from the corrosive fluids. If the schmoo depositiondescribed above is present on the internal surfaces, it does not allowthe dosed corrosion inhibitor to effectively coat and protect theequipment.

What is needed is a means to chemically remove and keep schmoo fromdepositing on the internal surfaces of production equipment whileinhibiting corrosion to help maintain the integrity of the equipment.

SUMMARY OF THE INVENTION

A composition is provided for inhibiting corrosion and/or removinghydrocarbonaceous deposits from equipment used in oil and gasapplications, the composition comprising a polyamine sulfonic acid salt.

The polyamine sulfonic acid salt can be formed by reaction of apolyamine component with a sulfonic acid component.

The polyamine component can comprise a polyalkylene polyamine havingfrom about three to about ten nitrogen atoms per molecule. Polyaminescontaining four or more nitrogen atoms per molecule are generallyavailable as mixtures of linear, branched, and cyclic compounds, most ofwhich contain the same number of nitrogen atoms.

The polyalkylene component can be a polyethylene polyamine, apolypropylene polyamine, a polybutylene polyamine, and combinationsthereof.

Preferably, the polyamine component comprises a mixture oftetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andhexaethyleneheptamine (HEHA).

The sulfonic acid salt component is selected from the group consistingof an aryl sulfonic acid, an alkyl sulfonic acid, an arylalkyl sulfonicacid, and combinations thereof.

Preferably, the organic sulfonic acid component is an aryl sulfonic acidcomprising linear and/or branched dodecylbenzenesulfonic acid.

The composition can further comprise a corrosion inhibitor component,including an imidazoline of Formula (I) or an imidazolinium salt ofFormula (II),

wherein R¹⁰ is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R¹¹ and R¹⁴are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆arylalkyl; R¹² and R¹³ are independently a C₁-C₆ alkyl group orhydrogen; X⁻ is chloride, bromide, iodide, carbonate, sulfonate,phosphate or an anion of an organic carboxylic acid including, but notlimited to, acetate; or a tautomer thereof.

Preferably, the corrosion inhibitor component is an imidazolinium saltof Formula (II) wherein R¹⁰ is an alkyl mixture typical in tall oilfatty acid (TOFA); R¹¹ is benzyl; R¹² and R¹³ are each hydrogen, R¹⁴ ishydroxyethyl, and X⁻ is chloride.

The corrosion inhibitor component can include a pyridinium salt ofFormula (III),

wherein R⁹ is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atoms, and X⁻is chloride, bromide, or iodide. Preferably, the corrosion inhibitorcomponent is a pyridinium salt of Formula (III), wherein R⁹ is benzyl,and X⁻ is chloride.

The corrosion inhibitor component can include an ethoxylated amine. Theethoxylated amine can be ethoxylated tallow amine.

The composition can further comprise a synergist. The synergist can beselected from the group consisting of thioglycolic acid,3,3′-dithiodipropionic acid, thiosulfate, thiourea, 2-mercaptoethanol,L-cysteine, tert-butyl mercaptan, and combinations thereof. Thesynergist can be 2-mercaptoethanol.

The composition can further comprise an alcoholic solvent, including butnot limited to, methanol.

The composition provides at least 95% corrosion protection after 12hours, 18 hours, or 24 hours for a 1018 carbon steel working electrodein a bubble test, wherein the bubble test is characterized by: (a) atesting temperature of about 60° C.; (b) a carbon dioxide saturatedliquid medium of 10% field crude oil and 90% synthetic brine; and (c) aninhibitor dosage of 20 ppm based on total fluids. The composition canprovide 98% protection after 12 hours, 18 hours, or 24 hours.

The composition provides greater than or equal to 40% schmoo removal ina Dynamic Schmoo Removal Loop (“DSRL”) test conducted at a dosage of 500or 1,000 ppm in brine at 122° F. The composition can provide greaterthan or equal to 60% schmoo removal in a Dynamic Schmoo Removal Loop(“DSRL”) test conducted at a dosage of 1,000 ppm in brine at 122° F.

The cleaner/corrosion inhibitor composition can comprise: (i) apolyamine sulfonic acid salt comprising at least one salt selected froma tetraethylenepentamine dodecylbenzenesulfonic acid salt, apentaethylenehexamine dodecylbenzenesulfonic acid salt, and ahexaethyleneheptamine dodecylbenzenesulfonic acid salt; (ii)2-mercaptoethanol; and (ii) methanol. Optionally, the cleaner/corrosioninhibitor composition can further comprise a corrosion inhibitorcomponent comprising an imidazolinium salt (e.g.,1-benzyl-1-(2-hydroxyethyl)-2-tall oil-2-imidazolinium chloride), apyridinium salt (e.g., benzyl pyridinium chloride), and an ethoxylatedalkyl amine (e.g., ethoxylated tallow amine). The cleaner/corrosioninhibitor composition can comprise a mixture of a tetraethylenepentaminedodecylbenzenesulfonic acid salt, a pentaethylenehexaminedodecylbenzenesulfonic acid salt, and a hexaethyleneheptaminedodecylbenzenesulfonic acid salt.

The composition can comprise 35 wt. % polyamine sulfonic acid salt, 8wt. % of a synergist, and 57 wt. % solvent, based on total weight of thecomposition.

Preferably, the composition comprises 35 wt. % of polyamine sulfonicacid salt, 15 wt. % of a corrosion inhibitor component, 8 wt. % of2-mercaptoethanol, and 42 wt. % methanol based on total weight of thecomposition.

A method of inhibiting corrosion at a surface and/or removinghydrocarbonaceous deposits from a surface is also provided. The methodcomprises contacting a surface with an effective amount of acleaner/corrosion inhibitor composition.

A method of preparing a cleaner/corrosion inhibitor composition is alsoprovided. The method comprises combining a polyamine component and asulfonic acid component to provide a polyamine sulfonic acid salt; andcombining the polyamine sulfonic acid salt component and a synergist,optionally at least one corrosion inhibitor component, and optionally atleast one solvent. The polyamine component can comprise atetraethylenepentamine, a pentaethylenehexamine, ahexaethyleneheptamine, and combinations thereof. The sulfonic acidcomponent can be linear or branched dodecylbenzenesulfonic acid or acombination thereof.

Other objects and features will be in part apparent and in part pointedout hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the corrosion rate versus time.

FIG. 2 is a graph of the % mass versus concentration of the composition.

DETAILED DESCRIPTION

Disclosed herein are cleaner/corrosion inhibitor compositions, methodsof using said compositions, and processes for their preparation. Thecompositions are useful in crude oil based and natural gas basedproducts, processes, and refinery streams. The described compositionsare particularly effective for inhibiting corrosion of mild steel inhydrocarbon, oil/brine mixtures, and aqueous systems. The compositionsare also particularly useful for removing hydrocarbonaceous deposits(e.g., schmoo) from metallic or mineral surfaces in contact with a fluidin oil and gas applications. The compositions can be used in sweetsystems (i.e., systems having a relatively high carbon dioxideconcentration) or in systems having sour conditions (i.e., relativelyhigh hydrogen sulfide concentration). The compositions are useful in awide range of climates and under a wide range of process conditions,(e.g., 0° C. to 200° C.), where other available cleaner/corrosioninhibitor compositions fail.

The control and prevention of schmoo is difficult. Schmoo deposits aresticky and difficult to clean, particularly near welds. Currently,commercially available cleaners for removing schmoo from equipment usedin oil and gas applications suffer from charge repulsive interactions atthe surface interfaces and provide only limited cleaning ability.

The disclosed compositions comprise a salt resulting from combination ofa polyamine component and a sulfonic acid component. Without being boundby theory, it is believed that the unexpected, superior cleaningperformance of the disclosed compositions result from reduced chargerepulsion at treated surfaces (e.g., interior of pipeline, dirtyproduction equipment). The salt, in addition to cleaning performance,may act as a corrosion inhibitor.

1. DEFINITION OF TERMS

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. In case of conflict, the present document, includingdefinitions, will control. Preferred methods and materials are describedbelow, although methods and materials similar or equivalent to thosedescribed herein can be used in practice or testing of the presentinvention. All publications, patent applications, patents and otherreferences mentioned herein are incorporated by reference in theirentirety. The materials, methods, and examples disclosed herein areillustrative only, and not intended to be limiting.

The terms “comprise(s),” “include(s),” “having,” “has,” “can,”“contain(s),” and variants thereof, as used herein, are intended to beopen-ended transitional phrases, terms, or words that do not precludethe possibility of additional acts or structures. The singular forms“a,” “and” and “the” include plural references unless the contextclearly dictates otherwise. The present disclosure also contemplatesother embodiments “comprising,” “consisting of” and “consistingessentially of,” the embodiments or elements presented herein, whetherexplicitly set forth or not.

The term “suitable substituent,” as used herein, is intended to mean achemically acceptable functional group, preferably a moiety that doesnot negate the activity of the inventive compounds. Such suitablesubstituents include, but are not limited to halo groups, perfluoroalkylgroups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynylgroups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups,alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxygroups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxygroups, HO—(C═O)— groups, heterocylic groups, cycloalkyl groups, aminogroups, alkyl- and dialkylamino groups, carbamoyl groups, alkylcarbonylgroups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups,alkylsulfonyl groups, and arylsulfonyl groups. Those skilled in the artwill appreciate that many substituents can be substituted by additionalsubstituents.

The term “alkyl,” as used herein, refers to a linear or branchedhydrocarbon radical, preferably having 1 to 32 carbon atoms (i.e., 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons). Alkyl groupsinclude, but are not limited to, methyl, ethyl, n-propyl, isopropyl,n-butyl, iso-butyl, secondary-butyl, and tertiary-butyl. Alkyl groupscan be unsubstituted or substituted by one or more suitablesubstituents, as defined above.

The term “alkenyl,” as used herein, refers to a straight or branchedhydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39,30, 31, or 32 carbons, and having one or more carbon-carbon doublebonds. Alkenyl groups include, but are not limited to, ethenyl,1-propenyl, 2-propenyl (allyl), isopropenyl, 2-methyl-1-propenyl,1-butenyl, and 2-butenyl. Alkenyl groups can be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkynyl,” as used herein, refers to a straight or branchedhydrocarbon radical, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39,30, 31, or 32 carbons, and having one or more carbon-carbon triplebonds. Alkynyl groups include, but are not limited to, ethynyl,propynyl, and butynyl. Alkynyl groups can be unsubstituted orsubstituted by one or more suitable substituents, as defined above.

The term “alkoxy,” as used herein, refers to an alkyl group, as definedherein, appended to the parent molecular moiety through an oxygen atom.

The term “aryl,” as used herein, means monocyclic, bicyclic, ortricyclic aromatic radicals such as phenyl, naphthyl,tetrahydronaphthyl, indanyl and the like; optionally substituted by oneor more suitable substituents, preferably 1 to 5 suitable substituents,as defined above.

The term “carbonyl,” “(C═O)” or “—C(O)—” (as used in phrases such asalkylcarbonyl, alkyl —(C═O)— or alkoxycarbonyl) refers to the joinder ofthe >C═O moiety to a second moiety such as an alkyl or amino group (i.e.an amido group). Alkoxycarbonylamino (i.e., alkoxy(C═O)—NH—) refers toan alkyl carbamate group. The carbonyl group is also equivalentlydefined herein as (C═O). Alkylcarbonylamino refers to groups such asacetamide.

The term “cycloalkyl”, as used herein, refers to a mono, bicyclic ortricyclic carbocyclic radical (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclopentenyl, cyclohexane, bicyclo[2.2.1]heptanyl,bicyclo[3.2.1]octanyl and bicyclo[5.2.0]nonanyl, etc.); optionallycontaining 1 or 2 double bonds. Cycloalkyl groups can be unsubstitutedor substituted by one or more suitable substituents, preferably 1 to 5suitable substituents, as defined above.

The term “halo” or “halogen,” as used herein, refers to a fluoro,chloro, bromo or iodo radical.

The term “heteroaryl,” as used herein, refers to a monocyclic, bicyclic,or tricyclic aromatic heterocyclic group containing one or moreheteroatoms selected from O, S and N in the ring(s). Heteroaryl groupsinclude, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl,pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, oxazolyl (e.g.,1,3-oxazolyl, 1,2-oxazolyl), thiazolyl (e.g., 1,2-thiazolyl,1,3-thiazolyl), pyrazolyl, tetrazolyl, triazolyl (e.g., 1,2,3-triazolyl,1,2,4-triazolyl), oxadiazolyl (e.g., 1,2,3-oxadiazolyl), thiadiazolyl(e.g., 1,3,4-thiadiazolyl), quinolyl, isoquinolyl, benzothienyl,benzofuryl, and indolyl. Heteroaryl groups can be unsubstituted orsubstituted by one or more suitable substituents, preferably 1 to 5suitable substituents, as defined above.

The term “heterocycle,” as used herein, refers to a monocyclic,bicyclic, or tricyclic group containing 1 to 4 heteroatoms selected fromN, O, S(O)_(n), P(O)_(n), PR^(x), NH or NR^(x), wherein R^(x) is asuitable substituent. Heterocyclic groups optionally contain 1 or 2double bonds. Heterocyclic groups include, but are not limited to,azetidinyl, tetrahydrofuranyl, imidazolidinyl, pyrrolidinyl,piperidinyl, piperazinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl,thiomorpholinyl, tetrahydrothiazinyl, tetrahydrothiadiazinyl,morpholinyl, oxetanyl, tetrahydrodiazinyl, oxazinyl, oxathiazinyl,indolinyl, isoindolinyl, quinuclidinyl, chromanyl, isochromanyl, andbenzoxazinyl. Examples of monocyclic saturated or partially saturatedring systems are tetrahydrofuran-2-yl, tetrahydrofuran-3-yl,imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl,pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-1-yl,piperidin-2-yl, piperidin-3-yl, piperazin-1-yl, piperazin-2-yl,piperazin-3-yl, 1,3-oxazolidin-3-yl, isothiazolidine,1,3-thiazolidin-3-yl, 1,2-pyrazolidin-2-yl, 1,3-pyrazolidin-1-yl,thiomorpholin-yl, 1,2-tetrahydrothiazin-2-yl,1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazinyl, morpholinyl,1,2-tetrahydrodiazin-2-yl, 1,3-tetrahydrodiazin-1-yl, 1,4-oxazin-2-yl,and 1,2,5-oxathiazin-4-yl. Heterocyclic groups can be unsubstituted orsubstituted by one or more suitable substituents, preferably 1 to 3suitable substituents, as defined above.

The term “hydroxy,” as used herein, refers to an —OH group.

The term “oxo,” as used herein, refers to a double bonded oxygen (═O)radical wherein the bond partner is a carbon atom. Such a radical canalso be thought as a carbonyl group.

The term “counterion,” as used herein, means a halide (e.g., fluoride,chloride, bromide, iodide), a carboxylate anion, such as selected fromdeprotonation of mineral acid, acrylic acid, acetic acid, methacrylicacid, glycolic acid, thioglycolic acid, propionic acid, butyric acid,and the like, or any other anionic constituent that satisfies the chargebalance necessary to form a neutral molecule.

The term “sweetening,” as used herein, can refer to a process thatremoves sulfur species from a gas or liquid. The sulfur species caninclude hydrogen sulfide and mercaptans.

The term “sour gas,” as used herein, can refer to a gas that includessignificant amounts of sulfur species, such as hydrogen sulfide and/ormercaptans.

The term “sour liquid” or “sour fluid,” as used herein, can refer to aliquid that includes significant amounts of sulfur species, such ashydrogen sulfide and/or mercaptans.

The term “water cut,” as used herein, means the percentage of water in acomposition containing an oil and water mixture.

The term “hydrocarbonaceous deposit,” as used herein, refers to anydeposit including at least one hydrocarbon constituent and forming onthe inner surface of flowlines, pipelines, injection lines, wellboresurfaces, storage tanks, process equipment, vessels, the like, and othercomponents in oil and gas applications. Such deposits also include“schmoo,” which refers to a solid, paste-like, or sludge-like substancethat adheres to almost any surface with which it comes in contact and isparticularly difficult to remove. Deposits contributing to schmoo caninclude, for example, sand, clays, sulfur, naphthenic acid salts,corrosion byproducts, biomass, and other hydrocarbonaceous materialsbound together with oil. These terms are used interchangeably herein.

The term “TOFA,” as used herein, refers to a tall oil fatty acid that isa distilled product derived from trees and includes a mixture of fattyacids.

The term “barrel” as used herein designates the standard 42 U.S. gallonbarrel commonly used as a measure in oil field practice.

The term “molar equivalent” as used herein is defined as the amount of asubstance which will either react with or supply one mole of hydrogenions (H+) in an acid-base reaction.

2. COMPOSITIONS

The cleaner/corrosion inhibitor compositions disclosed herein comprise apolyamine sulfonic acid salt. The compositions can further include oneor more additional corrosion inhibitors, synergists, and/or solvents.The compositions can provide both corrosion protection and a cleaningeffect for applications relating to the production, transportation,storage, and separation of crude oil and natural gas. In particular, thecompositions can improve production in an oil and/or gas application byreducing a corrosion rate of and/or removing hydrocarbonaceous deposits(e.g., schmoo) from metallic or mineral surfaces in contact with a fluidin oil and gas applications. The compositions can enhance oil and gasproduction by keeping surface facility equipment, pipelines, downholeinjection tubing and infrastructure, and pore throats around an injectorclean to accept an optimum water volume. The compositions can be used incontinuous and/or batch dosages to clean out process equipment that hasa tendency to accumulate deposits.

The polyamine sulfonic acid salt results from a synergistic combinationof a polyamine component and a sulfonic acid component. Without beingbound by theory, it is believed that the unexpected superior cleaningperformance of the disclosed compositions can be a result of thesynergistic combination of the polyamine and sulfonic acid to provide asalt with reduced charge repulsion at treated surfaces (e.g.,pipelines); whereas currently available compositions suffer from chargerepulsive interactions at the surface interface and provide only limitedcleaning ability.

The compositions can provide greater than or equal to 90% corrosionprotection, greater than or equal to 95% corrosion protection, greaterthan or equal to 96% corrosion protection, greater than or equal to 97%corrosion protection, greater than or equal to 98% corrosion protection,greater than or equal to 99% corrosion protection, or 100% corrosionprotection. The compositions can provide at least 98% corrosionprotection after 12 hours, at least 98% corrosion protection after 18hours, and/or at least 98% corrosion protection after 20 hours for acarbon steel working electrode (e.g., a 1018 carbon steel workingelectrode) in a bubble test, wherein the bubble test is characterized bya testing temperature of about 60° C.; a carbon dioxide saturated liquidmedium of 10% field crude oil and 90% synthetic brine; and an inhibitordosage of 20 ppm based on total fluids. The composition can provideabout 98.5% corrosion protection after 12 hours, about 98.3% corrosionprotection after 18 hours, and about 98.5% corrosion protection after 20hours. The composition can provide about 98.6% corrosion protectionafter 12 hours, about 98.1% corrosion protection after 18 hours, andabout 98.2% corrosion protection after 20 hours.

The compositions can provide a percent mass removal of hydrocarbonaceousdeposits from an apparatus, the percent mass removal greater than orequal to 10%, greater than or equal to 20%, greater than or equal to30%, greater than or equal to 40%, greater than or equal to 50%, orgreater than or equal to 60%. Dosed at 50 ppm, the compositions canprovide a percent mass removal of greater than or equal to 8%. Dosed at100 ppm, the compositions can provide a percent mass removal of greaterthan or equal to 13%. Dosed at 200 ppm, the compositions can provide apercent mass removal of greater than or equal to 21%. Dosed at 500 ppm,the compositions can provide a percent mass removal of greater than orequal to 49%. Dosed at 1,000 ppm, the compositions can provide a percentmass removal of greater than or equal to 61%. In a flow test, known as aDynamic Schmoo Removal Loop (“DSRL”), conducted at dosages of 50, 100,200, 500, or 1,000 ppm in brine at 122° F., the compositions can providea percent schmoo removal of greater than or equal to 10%, greater thanor equal to 20%, greater than or equal to 30%, greater than or equal to40%, greater than or equal to 50%, or greater than or equal to 60%.

(a) Polyamine Sulfonic Acid Salt

The compositions disclosed herein comprise a polyamine sulfonic acidsalt formed by reaction of a polyamine component with a sulfonic acidcomponent. The polyamine sulfonic acid salt can act as a corrosioninhibitor, a cleaner, or both.

The molar equivalent ratio of the polyamine component to the sulfonicacid component can range from 1:1 to 1:3. For example, the polyaminesulfonic acid salt can comprise one molar equivalent of the polyaminecomponent and one molar equivalent of the sulfonic acid component, onemolar equivalent of the polyamine component and two molar equivalents ofthe sulfonic acid component, or one molar equivalent of the polyaminecomponent and three molar equivalents of the sulfonic acid component.

The components of the polyamine sulfonic acid salt can also bedetermined as a weight ratio. The weight ratio of the polyaminecomponent to the sulfonic acid component can range from 1:2 to 2:1, andpreferably from 1:1 to 1:1.5.

The polyamine sulfonic acid salt component can comprise a singlepolyamine sulfonic acid salt, or can comprise a mixture of polyaminesulfonic acid salts. The polyamine sulfonic acid salt componentcomprises a tetraethylenepentamine dodecylbenzenesulfonic acid salt, apentaethylenehexamine dodecylbenzenesulfonic acid salt, ahexaethyleneheptamine dodecylbenzenesulfonic acid salt, or anycombination thereof. The dodecylbenzenesulfonic acid can be a lineardodecylbenzenesulfonic acid, a branched dodecylbenzenesulfonic acid, ora combination thereof.

The polyamine sulfonic acid salt component can be present in thecompositions in an amount ranging from about 10 wt. % to about 70 wt. %,based on total weight of the composition. The polyamine sulfonic acidsalt component can constitute 25 wt % to 45 wt % of thecleaner/corrosion inhibitor composition, based on total weight of thecomposition. The polyamine sulfonic acid salt component can constituteabout 25 wt %, about 26 wt %, about 27 wt %, about 28 wt %, about 29 wt%, about 30 wt %, about 31 wt %, about 32 wt %, about 33 wt %, about 34wt %, about 35 wt %, about 36 wt %, about 37 wt %, about 38 wt %, about39 wt %, about 40 wt %, about 41 wt %, about 42 wt %, about 43 wt %,about 44 wt %, or about 45 wt % of the cleaner/corrosion inhibitorcomposition, based on total weight of the composition. Preferably, thepolyamine sulfonic acid salt component is present in an amount of about35 wt. %, based on total weight of the composition.

The composition can comprise from about 10 to about 70 wt. % of thepolyamine sulfonic acid salt based on total weight of the composition.Preferably, the composition comprises from about 25 to about 45 wt. % ofthe polyamine sulfonic acid salt. More preferably, the compositioncomprises from about 30 to about 40 wt. % of the polyamine sulfonic acidsalt. Even more preferably, the composition comprises 35 wt. % of thepolyamine sulfonic acid salt.

i. Polyamine Component

The polyamine component of the polyamine sulfonic acid salt componentcan constitute 5 wt % to 50 wt % of the cleaner/corrosion inhibitorcomposition, based on total weight of the composition. The polyamine(s)can constitute 10 wt % to 30 wt % of the cleaner/corrosion inhibitorcomposition, based on total weight of the composition. The polyamine(s)can constitute about 10 wt %, about 11 wt %, about 12 wt %, about 13 wt%, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt %, about 18wt %, about 19 wt %, about 20 wt %, about 21 wt %, about 22 wt %, about23 wt %, about 24 wt %, about 25 wt %, about 26 wt %, about 27 wt %,about 28 wt %, about 29 wt %, or about 30 wt % of the cleaner/corrosioninhibitor composition, based on total weight of the composition. Thepolyamine(s) can constitute 20 wt % of the cleaner/corrosion inhibitorcomposition, based on total weight of the composition.

The polyamine component can constitute 20 wt % to 70 wt % of thepolyamine sulfonic acid salt formed from the polyamine component and thesulfonic acid component, based on total weight of the polyamine sulfonicacid salt component. The polyamine(s) can constitute 35 wt % to 75 wt %of the polyamine sulfonic acid salt formed from the polyamine componentand the sulfonic acid component, based on total weight of the polyaminesulfonic acid salt. The polyamine(s) can constitute about 35 wt %, about36 wt %, about 37 wt %, about 38 wt %, about 39 wt %, about 40 wt %,about 41 wt %, about 42 wt %, about 43 wt %, about 44 wt %, about 45 wt%, about 46 wt %, about 47 wt %, about 48 wt %, about 49 wt %, about 50wt %, about 51 wt %, about 52 wt %, about 53 wt %, about 54 wt %, about55 wt %, about 56 wt %, about 57 wt %, about 58 wt %, about 59 wt %,about 60 wt %, about 61 wt %, about 62 wt %, about 63 wt %, about 64 wt%, about 65 wt %, about 66 wt %, about 67 wt %, about 68 wt %, about 69wt %, about 70 wt %, about 71 wt %, about 72 wt %, about 73 wt %, about74 wt %, or about 75 wt % of the polyamine sulfonic acid salt componentformed from the polyamine component and the sulfonic acid component,based on total weight of the polyamine sulfonic acid salt component. Thepolyamine(s) can constitutes about 57 wt % of the polyamine sulfonicacid salt component formed from the polyamine component and the sulfonicacid component, based on total weight of the polyamine sulfonic acidsalt component.

The polyamine component can be a composition of one or more polyamines.The polyamine component can comprise a polyalkylene polyaminePolyalkylene polyamine compounds can include, but are not limited topolyethylene polyamines, polypropylene polyamines, polybutylenepolyamines and combinations thereof.

Suitable polyethylene polyamines include, but not limited to, diethylenetriamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine(TEPA), pentaethylene hexamine (PEHA), hexaethylene heptamine (HEHA),and higher homologues.

Suitable polypropylene polyamines include, but not limited to,dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine,pentapropylene hexamine, hexapropylene heptamine, and higher homologues.

Suitable polybutylene polyamines include, but are not limited to,dibutylene triamine, tributylene tetramine, tetrabutylene pentamine,pentabutylene hexamine, hexabutylene heptamine, and higher homologues.

Other suitable polyalkylene polyamines includebis(hexamethylene)triamine, N,N′-bis(3-aminopropyl)ethylenediamine,spermidine, and spermine.

It will be recognized by those skilled in the art that polyalkylenepolyamines containing four or more nitrogen atoms are generallyavailable as mixtures of linear, branched, and cyclic compounds, most ofwhich contain the same number of nitrogen atoms. For example,triethylene tetramine (TETA) contains not only linear TETA, but alsotris(aminoethyl)amine, N,N′-bis(2-aminoethyl)piperazine, andN-[(2-aminoethyl)-2-aminoethyl]piperazine. Similarly, tetraethylenepentamine is principally a mixture of four TEPA ethyleneamines,including linear, branched, and two cyclic TEPA products.

A preferred polyalkylene polyamine is Ethyleneamine E-100, acommercially available mixture of polyethylene polyamines comprisingTEPA, PEHA, and HEHA (Huntsman Corporation). Ethyleneamine E-100typically consists of less than 1.0 wt. % of low molecular weight amine,10-15 wt. % TEPA, 40-50 wt. % PEHA, and the balance HEHA and higheroligomers. Typically, Ethyleneamine E-100 has total nitrogen content ofabout 33-34 wt. % and a number average molecular weight of 250-300g/mole.

A suitable polyamine mixture is Heavy Polyamine X (HPA-X), commerciallyavailable from Dow Chemical Company. Heavy Polyamine X is a complexmixture of linear, branched, and cyclic polyethylene polyamines,comprising TETA, TEPA, PEHA, and polyethylene polyamines (CAS No.68131-73-7 or CAS No. 29320-38-5).

Another suitable polyamine mixture is Amix 1000 (CAS #68910-05-4),commercially available from BASF Corporation Amix 1000 is a mixture ofroughly equivalent amounts of aminoethylethanolamine, triethylenetetramine (TETA), aminoethylpiperazine, and high boiling polyamines.

The polyamine component can comprise an etheramine, a polyetheramine,and combinations thereof. A suitable etheramine, for example, is2-(2-(dimethylamino)ethoxy)-ethanol (CAS #1704-62-7), which can be usedalone or as a commercially available mixture. Preferably, the etheramineis BASF Amix DAS, which comprises 20-80 wt. % of2-(2-(dimethylamino)ethoxy)ethanol, 5-60 wt. % of2-dimethylaminoethanol, <8 wt. % of ethyleneglycol, and <6 wt. % of2-(ethenyloxy)ethanol.

Exemplary polyetheramines include, but are not limited to,Polyetheramine D230, Polyetheramine D400, Polyetheramine D2000,Polyetheramine T403, Polyetheramine T5000, all of which are commerciallyavailable from BASF Corporation.

ii. Sulfonic Acid Component

The sulfonic acid component of the polyamine sulfonic acid saltcomponent can constitute 5 wt % to 50 wt % of the cleaner/corrosioninhibitor composition, based on total weight of the composition. Thesulfonic acid(s) can constitute 5 wt % to 25 wt % of thecleaner/corrosion inhibitor composition, based on total weight of thecomposition. The sulfonic acid(s) can constitute about 5 wt %, about 6wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, about 11wt %, about 12 wt %, about 13 wt %, about 14 wt %, about 15 wt %, about16 wt %, about 17 wt %, about 18 wt %, about 19 wt %, about 20 wt %,about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt %, or about 25wt % of the cleaner/corrosion inhibitor composition, based on totalweight of the composition. The sulfonic acid(s) can constitute 15 wt %of the cleaner/corrosion inhibitor composition, based on total weight ofthe composition.

The sulfonic acid component can constitute 20 wt % to 70 wt % of thepolyamine sulfonic acid salt component formed from the polyaminecomponent and the sulfonic acid component, based on total weight of thepolyamine sulfonic acid salt component. The sulfonic acid component canconstitute 35 wt % to 75 wt % of the polyamine sulfonic acid saltcomponent formed from the polyamine component and the sulfonic acidcomponent, based on total weight of the polyamine sulfonic acid saltcomponent. The sulfonic acid component can constitute about 20 wt %,about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt%, about 26 wt %, about 27 wt %, about 28 wt %, about 29 wt %, about 30wt %, about 31 wt %, about 32 wt %, about 33 wt %, about 34 wt %, about35 wt %, about 36 wt %, about 37 wt %, about 38 wt %, about 39 wt %,about 40 wt %, about 41 wt %, about 42 wt %, about 43 wt %, about 44 wt%, about 45 wt %, about 46 wt %, about 47 wt %, about 48 wt %, about 49wt %, about 50 wt %, about 51 wt %, about 52 wt %, about 53 wt %, about54 wt %, about 55 wt %, about 56 wt %, about 57 wt %, about 58 wt %,about 59 wt %, or about 60 wt % of the polyamine sulfonic acid saltcomponent formed from the polyamine component and the sulfonic acidcomponent, based on total weight of the polyamine sulfonic acid saltcomponent. The sulfonic acid component can constitute about 42 wt % ofthe polyamine sulfonic acid salt component formed from the polyaminecomponent and the sulfonic acid component, based on total weight of thepolyamine sulfonic acid salt component.

The sulfonic acid component can be a composition of one or more sulfonicacid compounds. For example, the sulfonic acid component can compriseone or more organic sulfonic acids. The organic sulfonic acid can be anaryl sulfonic acid, including but not limited to a linearalkylbenzenesulfonic acid, a branched alkylbenzenesulfonic acids, andother substituted or unsubstituted aromatic sulfonic acids. Suitablearyl sulfonic acids include, but are not limited to, methylbenzenesulfonic acid (e.g., p-toluenesulfonic acid), ethylbenzene sulfonicacid, butylbenzene sulfonic acid, octylbenzene sulfonic acid,dodecylbenzene sulfonic acid, and 2-naphthalene sulfonic acid.Preferably, the aryl sulfonic acid is a linear or brancheddodecylbenzenesulfonic acid.

The organic sulfonic acid can also be an alkyl sulfonic acid or anarylalkyl sulfonic acid, including but not limited to methanesulfonicacid, trifluoromethanesulfonic acid, DL-camphorsulfonic acid, andphenylmethanesulfonic acid.

The organic sulfonic acid can be a monosulfonic acid, a disulfonic acid,or a polysulfonic acid. Suitable disulfonic acids include, but are notlimited to, benzenedisulfonic acid, napthalenedisulfonic acid,2,3-dimethyl-1,4-benzenedisulfonic acid,2,4-dimethyl-1,3-benzenedisulfonic acid,2,5-dimethyl-1,3-benzenedisulfonic acid,2,5-dimethyl-1,4-benzenedisulfonic acid,3,6-dimethyl-1,2-benzenedisulfonic acid, or a combination thereof.Suitable polysulfonic acids include, but are not limited to, benzenetrisulfonic acid, naphthalene trisulfonic acid,1,3,6-napthalenetrisulfonic acid, 1-nitronaphthalene-3,6,8-trisulfonicacid, or a combination thereof.

(b) Corrosion Inhibitor Component

The compositions disclosed herein may include a corrosion inhibitorcomponent comprised of one or more corrosion inhibitors. The corrosioninhibitor(s) may be present in an amount of 5 wt % to 50 wt %, based ontotal weight of the composition. The corrosion inhibitor(s) canconstitute 5 wt % to 25 wt % of the cleaner/corrosion inhibitorcomposition, based on total weight of the composition. The corrosioninhibitor(s) can constitute about 5 wt %, about 6 wt %, about 7 wt %,about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt %,about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17 wt%, about 18 wt %, about 19 wt %, about 20 wt %, about 21 wt %, about 22wt %, about 23 wt %, about 24 wt %, or about 25 wt % of thecleaner/corrosion inhibitor composition, based on total weight of thecomposition. Preferably, the compositions comprise about 15 wt % of thecorrosion inhibitor(s), based on total weight of the composition.

Suitable corrosion inhibitors include, but are not limited to, alkyl,hydroxyalkyl, alkylaryl, arylalkyl or arylamine quaternary salts; monoor polycyclic aromatic amine salts; imidazoline derivatives; mono-, di-or trialkyl or alkylaryl phosphate esters; phosphate esters ofhydroxylamines; phosphate esters of polyols; and monomeric or oligomericfatty acids.

Suitable alkyl, hydroxyalkyl, alkylaryl arylalkyl or arylaminequaternary salts include those alkylaryl, arylalkyl and arylaminequaternary salts of the formula [N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻] whereinR^(5a), R^(6a), R^(7a), and R^(8a) contain one to 18 carbon atoms, and Xis Cl, Br or I. For the quaternary salts, R^(5a), R^(6a), R^(7a), andR^(8a) can each be independently selected from the group consisting ofalkyl (e.g., C₁-C₁₈ alkyl), hydroxyalkyl (e.g., C₁-C₁₈ hydroxyalkyl),and arylalkyl (e.g., benzyl). The mono or polycyclic aromatic amine saltwith an alkyl or alkylaryl halide include salts of the formula[N⁺R^(5a)R^(6a)R^(7a)R^(8a)][X⁻] wherein R^(5a), R^(6a), R^(7a), andR^(8a) contain one to 18 carbon atoms, and X is Cl, Br or I.

Suitable quaternary ammonium salts include, but are not limited to,tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrapropylammonium chloride, tetrabutyl ammonium chloride, tetrahexyl ammoniumchloride, tetraoctyl ammonium chloride, benzyltrimethyl ammoniumchloride, benzyltriethyl ammonium chloride, phenyltrimethyl ammoniumchloride, phenyltriethyl ammonium chloride, cetyl benzyldimethylammonium chloride, hexadecyl trimethyl ammonium chloride, dimethyl alkylbenzyl quaternary ammonium compounds, monomethyl dialkyl benzylquaternary ammonium compounds, trimethyl benzyl quaternary ammoniumcompounds, and trialkyl benzyl quaternary ammonium compounds, whereinthe alkyl group can contain between about 6 and about 24 carbon atoms,about 10 and about 18 carbon atoms, or about 12 to about 16 carbonatoms. The quaternary ammonium salt can be an alkylamine benzylquaternary ammonium salt, a benzyl triethanolamine quaternary ammoniumsalt, or a benzyl dimethylaminoethanolamine quaternary ammonium salt.

The corrosion inhibitor component can comprise a quaternary ammoniumsalt or pyridinium salt such as those represented by Formula (III):

wherein R⁹ is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atoms and X⁻ ischloride, bromide, or iodide. Among these compounds are alkyl pyridiniumsalts and alkyl pyridinium benzyl quats. Exemplary compounds includemethylpyridinium chloride, ethyl pyridinium chloride, propyl pyridiniumchloride, butyl pyridinium chloride, octyl pyridinium chloride, decylpyridinium chloride, lauryl pyridinium chloride, cetyl pyridiniumchloride, benzyl pyridinium and an alkyl benzyl pyridinium chloride,preferably wherein the alkyl is a C₁-C₆ hydrocarbyl group. Preferably,the corrosion inhibitor component includes benzyl pyridinium chloride.

The quaternary ammonium salt or pyridinium salt can constitute 0 wt % to100 wt % of the corrosion inhibitor component, based on total weight ofthe corrosion inhibitor component. The quaternary ammonium salt orpyridinium salt can constitute 20 wt % to 40 wt % of the corrosioninhibitor component, based on total weight of the corrosion inhibitorcomponent. The quaternary ammonium salt or pyridinium salt canconstitute about 20 wt %, about 21 wt %, about 22 wt %, about 23 wt %,about 24 wt %, about 25 wt %, about 26 wt %, about 27 wt %, about 28 wt%, about 29 wt %, about 30 wt %, about 31 wt %, about 32 wt %, about 33wt %, about 34 wt %, about 35 wt %, about 36 wt %, about 37 wt %, about38 wt %, about 39 wt %, or about 40 wt % of the corrosion inhibitorcomponent, based on total weight of the corrosion inhibitor component.Preferably, the quaternary ammonium salt or pyridinium salt constitutes31.23 wt. % of the corrosion inhibitor component, based on total weightof the corrosion inhibitor component.

The corrosion inhibitor component can comprise an imidazoline derivedfrom a diamine, such as ethylene diamine (EDA), diethylene triamine(DETA), triethylene tetraamine (TETA) etc. and a long chain fatty acidsuch as tall oil fatty acid (TOFA). Suitable imidazolines include thoseof Formula (I):

wherein R¹⁰ is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R¹¹ ishydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆ arylalkyl; and R¹²and R¹³ are independently a C₁-C₆ alkyl group or hydrogen. Preferably,the corrosion inhibitor is an imidazolidine wherein R¹⁰ is the alkylmixture typical in tall oil fatty acid (TOFA), and R¹¹, R¹² and R¹³ areeach hydrogen.

The corrosion inhibitor component can include an imidazolinium compoundof Formula (II):

wherein R¹⁰ is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R¹¹ and R¹⁴are independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆arylalkyl; R¹² and R¹³ are independently a C₁-C₆ alkyl group orhydrogen; and X⁻ is chloride, bromide, iodide, carbonate, sulfonate,phosphate, or the anion of an organic acid such as acetate. Preferably,the corrosion inhibitor component includes1-benzyl-1-(2-hydroxyethyl)-2-tall-oil-2-imidazolinium chloride.

The imidazoline and/or imidazolinium compound can comprise 0 to 100 wt.% of the corrosion inhibitor component, based on total weight of thecorrosion inhibitor component. The imidazoline and/or imidazoliniumcompound constitutes 20 wt % to 40 wt % of the corrosion inhibitorcomponent, based on total weight of the corrosion inhibitor component.The imidazoline and/or imidazolinium compound constitutes about 20 wt %,about 21 wt %, about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt%, about 26 wt %, about 27 wt %, about 28 wt %, about 29 wt %, about 30wt %, about 31 wt %, about 32 wt %, about 33 wt %, about 34 wt %, about35 wt %, about 36 wt %, about 37 wt %, about 38 wt %, about 39 wt %, orabout 40 wt % of the corrosion inhibitor component, based on totalweight of the corrosion inhibitor component. The imidazoline and/orimidazolinium compound can constitute 27.11 wt % of the corrosioninhibitor component, based on total weight of the corrosion inhibitorcomponent.

Suitable mono-, di- and trialkyl as well as alkylaryl phosphate estersand phosphate esters of mono, di, and triethanolamine typically containbetween from 1 to about 18 carbon atoms. Preferred mono-, di- andtrialkyl phosphate esters, alkylaryl or arylalkyl phosphate esters arethose prepared by reacting a C₃-C₁₈ aliphatic alcohol with phosphorouspentoxide. The phosphate intermediate interchanges its ester groups withtriethyl phosphate with triethylphosphate producing a more broaddistribution of alkyl phosphate esters.

Alternatively, the phosphate ester can be made by admixing with an alkyldiester, a mixture of low molecular weight alkyl alcohols or diols. Thelow molecular weight alkyl alcohols or diols preferably include C₆ toC₁₀ alcohols or diols. Further, phosphate esters of polyols and theirsalts containing one or more 2-hydroxyethyl groups, and hydroxylaminephosphate esters obtained by reacting polyphosphoric acid or phosphoruspentoxide with hydroxylamines such as diethanolamine or triethanolamineare preferred.

The corrosion inhibitor component can include a monomeric or oligomericfatty acid. Preferred are C₁₄-C₂₂ saturated and unsaturated fatty acidsas well as dimer, trimer and oligomer products obtained by polymerizingone or more of such fatty acids.

The corrosion inhibitor component can comprise an ethoxylated amine. Theethoxylated amine can be an ethoxylated alkyl amine. The ethoxylatedamine can be ethoxylated tallow amine. The ethoxylated amine canconstitute 0 wt % to 70 wt % of the corrosion inhibitor component, basedon total weight of the corrosion inhibitor component. The ethoxylatedamine can constitute 20 wt % to 40 wt % of the corrosion inhibitorcomponent, based on total weight of the corrosion inhibitor component.The ethoxylated amine can constitute about 20 wt %, about 21 wt %, about22 wt %, about 23 wt %, about 24 wt %, about 25 wt %, about 26 wt %,about 27 wt %, about 28 wt %, about 29 wt %, about 30 wt %, about 31 wt%, about 32 wt %, about 33 wt %, about 34 wt %, about 35 wt %, about 36wt %, about 37 wt %, about 38 wt %, about 39 wt %, or about 40 wt % ofthe corrosion inhibitor component, based on total weight of thecorrosion inhibitor component. The ethoxylated amine can constitute27.06 wt % of the corrosion inhibitor component, based on total weightof the corrosion inhibitor component.

The corrosion inhibitor can comprise2-alkyl-1-benzyl-1-(2-hydroxyethyl)-2-imidazolium chlorides (e.g., C₁₂-,C₁₄-, C₁₆-, and/or C₁₈-alkyl-1-benzyl-1-(2-hydroxyethyl)-2-imidazoliumchlorides), N-benzylpyridinium chlorides (e.g., N-benzyl-pyridiniumchloride, N-benzyl-picolinium chloride), ethoxylated tallow amine, andcombinations thereof.

Preferably, the corrosion inhibitor comprises a mixture of1-benzyl-1-(2-hydroxyethyl)-2-tall oil-2-imidazolinium chloride (e.g.,about 27 wt. %), N-benzyl-pyridinium chloride (e.g., about 31 wt. %),and ethoxylated tallow amine (e.g., about 27 wt %).

(c) Synergist

The compositions disclosed herein can include a synergist. The synergistcan be present in an amount of 1 wt % to 20 wt %, based on total weightof the composition. The synergist can constitute about 1 wt %, about 2wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt%, about 8 wt %, about 9 wt %, about 10 wt %, about 11 wt %, about 12 wt%, about 13 wt %, about 14 wt %, about 15 wt %, about 16 wt %, about 17wt %, about 18 wt %, about 19 wt %, or about 20 wt % of thecleaner/corrosion inhibitor composition, based on total weight of thecomposition. The synergist can be present in an amount of about 8 wt %,based on total weight of the composition.

Suitable synergists include compounds that enhance the corrosioninhibiting and/or cleaning performance of the composition. The synergistcan be a sulfur-containing compound, including but not limited to,thioglycolic acid, 3,3′-dithiodipropionic acid, thiosulfate, thiourea,2-mercaptoethanol, L-cysteine, and tert-butyl mercaptan. Preferably, thesynergist is 2-mercaptoethanol.

(d) Solvent

The compositions disclosed herein can include a solvent. The solvent canbe present in an amount of 10 wt % to 80 wt %, based on total weight ofthe composition. The solvent can constitute 20 wt % to 60 wt % of thecleaner/corrosion inhibitor composition, based on total weight of thecomposition. The solvent can constitute about 20 wt %, about 21 wt %,about 22 wt %, about 23 wt %, about 24 wt %, about 25 wt %, about 26 wt%, about 27 wt %, about 28 wt %, about 29 wt %, about 30 wt %, about 31wt %, about 32 wt %, about 33 wt %, about 34 wt %, about 35 wt %, about36 wt %, about 37 wt %, about 38 wt %, about 39 wt %, about 40 wt %,about 41 wt %, about 42 wt %, about 43 wt %, about 44 wt %, about 45 wt%, about 46 wt %, about 47 wt %, about 48 wt %, about 49 wt %, about 50wt %, about 51 wt %, about 52 wt %, about 53 wt %, about 54 wt %, about55 wt %, about 56 wt %, about 57 wt %, about 58 wt %, about 59 wt %, orabout 60 wt % of the cleaner/corrosion inhibitor composition, based ontotal weight of the composition. The solvent can be present in an amountof about 42 wt %, based on total weight of the composition. The solventcan be methanol and is present in an amount of about 42 wt %, based ontotal weight of the composition.

Suitable solvents include, but are not limited to, alcohols,hydrocarbons, ketones, ethers, aromatics, amides, nitriles, sulfoxides,esters, and aqueous systems. The solvent can be water, isopropanol,methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene,ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethyleneglycol monoethyl ether, or xylene. Representative polar solventssuitable for formulation with the composition include water, brine,seawater, alcohols (including straight chain or branched aliphatic suchas methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol,hexanol, octanol, decanol, 2-butoxyethanol, etc.), glycols andderivatives (ethylene glycol, 1,2-propylene glycol, 1,3-propyleneglycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexanone,diisobutylketone), N-methylpyrrolidinone (NMP), N,N-dimethylformamide,and the like. Representative non-polar solvents suitable for formulationwith the composition include aliphatic hydrocarbons such as pentane,hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane,diesel, and the like; aromatic hydrocarbons such as toluene, xylene,heavy aromatic naphtha; and fatty acid derivatives (acids, esters,amides), and the like.

The solvent can be a solvent compatible with an arctic environment, asfor example, methanol.

The compositions of the invention can optionally include one or moreadditives. Suitable additives include, but are not limited to,asphaltene inhibitors, paraffin inhibitors, scale inhibitors,emulsifiers, water clarifiers, dispersants, emulsion breakers, hydrogensulfide scavengers, gas hydrate inhibitors, biocides, pH modifiers, andsurfactants.

(e) Asphaltene Inhibitors

Suitable asphaltene inhibitors include, but are not limited to,aliphatic sulfonic acids; alkyl aryl sulfonic acids; aryl sulfonates;lignosulfonates; alkylphenol/aldehyde resins and similar sulfonatedresins; polyolefin esters; polyolefin imides; polyolefin esters withalkyl, alkylenephenyl or alkylenepyridyl functional groups; polyolefinamides; polyolefin amides with alkyl, alkylenephenyl or alkylenepyridylfunctional groups; polyolefin imides with alkyl, alkylenephenyl oralkylenepyridyl functional groups; alkenyl/vinyl pyrrolidone copolymers;graft polymers of polyolefins with maleic anhydride or vinyl imidazole;hyperbranched polyester amides; polyalkoxylated asphaltenes, amphotericfatty acids, salts of alkyl succinates, sorbitan monooleate, andpolyisobutylene succinic anhydride.

(f) Paraffin Inhibitors

Suitable paraffin inhibitors include, but are not limited to, paraffincrystal modifiers, and dispersant/crystal modifier combinations.Suitable paraffin crystal modifiers include, but are not limited to,alkyl acrylate copolymers, alkyl acrylate vinylpyridine copolymers,ethylene vinyl acetate copolymers, maleic anhydride ester copolymers,branched polyethylenes, naphthalene, anthracene, microcrystalline waxand/or asphaltenes. Suitable dispersants include, but are not limitedto, dodecyl benzene sulfonate, oxyalkylated alkylphenols, andoxyalkylated alkylphenolic resins.

(g) Scale Inhibitors

Suitable scale inhibitors include, but are not limited to, phosphates,phosphate esters, phosphoric acids, phosphonates, phosphonic acids,polyacrylamides, salts of acrylamidomethyl propane sulfonate/acrylicacid copolymer (AMPS/AA), phosphinated maleic copolymer (PHOS/MA), andsalts of a polymaleic acid/acrylic acid/acrylamidomethyl propanesulfonate terpolymer (PMA/AA/AMPS).

(h) Emulsifiers

Suitable emulsifiers include, but are not limited to, salts ofcarboxylic acids, products of acylation reactions between carboxylicacids or carboxylic anhydrides and amines, and alkyl, acyl and amidederivatives of saccharides (alkyl-saccharide emulsifiers).

(i) Water Clarifiers

Suitable water clarifiers include, but are not limited to, inorganicmetal salts such as alum, aluminum chloride, and aluminum chlorohydrate,or organic polymers such as acrylic acid based polymers, acrylamidebased polymers, polymerized amines, alkanolamines, thiocarbamates, andcationic polymers such as diallyldimethylammonium chloride (DADMAC).

(j) Dispersants

Suitable dispersants include, but are not limited to, aliphaticphosphonic acids with 2-50 carbons, such as hydroxyethyl diphosphonicacid, and aminoalkyl phosphonic acids, e.g. polyaminomethylenephosphonates with 2-10 N atoms e.g. each bearing at least one methylenephosphonic acid group; examples of the latter are ethylenediaminetetra(methylene phosphonate), diethylenetriamine penta(methylenephosphonate), and the triamine- and tetramine-polymethylene phosphonateswith 2-4 methylene groups between each N atom, at least 2 of the numbersof methylene groups in each phosphonate being different. Other suitabledispersion agents include lignin, or derivatives of lignin such aslignosulfonate and naphthalene sulfonic acid and derivatives.

(k) Emulsion Breakers

Suitable emulsion breakers include, but are not limited to,dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonicacid (NAXSA), epoxylated and propoxylated compounds, anionic cationicand nonionic surfactants, and resins, such as phenolic and epoxideresins.

(l) Hydrogen Sulfide Scavengers

Suitable additional hydrogen sulfide scavengers include, but are notlimited to, oxidants (e.g., inorganic peroxides such as sodium peroxideor chlorine dioxide); aldehydes (e.g., of 1-10 carbons such asformaldehyde, glyoxal, glutaraldehyde, acrolein, or methacrolein; andtriazines (e.g., monoethanolamine triazine, monomethylamine triazine,and triazines from multiple amines or mixtures thereof).

(m) Gas Hydrate Inhibitors

Suitable gas hydrate inhibitors include, but are not limited to,thermodynamic hydrate inhibitors (THI), kinetic hydrate inhibitors(KHI), and anti-agglomerates (AA). Suitable thermodynamic hydrateinhibitors include, but are not limited to, sodium chloride, potassiumchloride, calcium chloride, magnesium chloride, sodium bromide, formatebrines (e.g. potassium formate), polyols (such as glucose, sucrose,fructose, maltose, lactose, gluconate, monoethylene glycol, diethyleneglycol, triethylene glycol, mono-propylene glycol, dipropylene glycol,tripropylene glycols, tetrapropylene glycol, monobutylene glycol,dibutylene glycol, tributylene glycol, glycerol, diglycerol,triglycerol, and sugar alcohols (e.g. sorbitol, mannitol)), methanol,propanol, ethanol, glycol ethers (such as diethyleneglycolmonomethylether, ethyleneglycol monobutylether), and alkyl or cyclicesters of alcohols (such as ethyl lactate, butyl lactate, methylethylbenzoate).

Suitable kinetic hydrate inhibitors and anti-agglomerates include, butare not limited to, polymers and copolymers, polysaccharides (such ashydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), starch,starch derivatives, and xanthan), lactams (such as polyvinylcaprolactam,polyvinyl lactam), pyrrolidones (such as polyvinyl pyrrolidone ofvarious molecular weights), surfactants (such as fatty acid salts,ethoxylated alcohols, propoxylated alcohols, sorbitan esters,ethoxylated sorbitan esters, polyglycerol esters of fatty acids, alkylglucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates,alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaine, alkylamido betaines), hydrocarbon based dispersants (such as lignosulfonates,iminodisuccinates, polyaspartates), amino acids, and proteins.

(n) Biocides

Suitable biocides include, but are not limited to, oxidizing andnon-oxidizing biocides. Suitable non-oxidizing biocides include, forexample, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein),amine-type compounds (e.g., quaternary amine compounds and cocodiamine),halogenated compounds (e.g., 2-bromo-2-nitropropane-3-diol (Bronopol)and 2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfur compounds (e.g.,isothiazolone, carbamates, and metronidazole), and quaternaryphosphonium salts (e.g., tetrakis(hydroxymethyl)-phosphonium sulfate(THPS)). Suitable oxidizing biocides include, for example, sodiumhypochlorite, trichloroisocyanuric acids, dichloroisocyanuric acid,calcium hypochlorite, lithium hypochlorite, chlorinated hydantoins,stabilized sodium hypobromite, activated sodium bromide, brominatedhydantoins, chlorine dioxide, ozone, and peroxides.

(o) pH Modifiers

Suitable pH modifiers include, but are not limited to, alkalihydroxides, alkali carbonates, alkali bicarbonates, alkaline earth metalhydroxides, alkaline earth metal carbonates, alkaline earth metalbicarbonates and mixtures or combinations thereof. Exemplary pHmodifiers include sodium hydroxide, potassium hydroxide, calciumhydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodiumbicarbonate, potassium bicarbonate, magnesium oxide, and magnesiumhydroxide.

(p) Surfactants

Suitable surfactants include, but are not limited to, anionicsurfactants, cationic surfactants, and nonionic surfactants. Anionicsurfactants include alkyl aryl sulfonates, olefin sulfonates, paraffinsulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylatesand alkyl ether carboxylates, and alkyl and ethoxylated alkyl phosphateesters, and mono and dialkyl sulfosuccinates and sulfosuccinamates.Cationic surfactants include alkyl trimethyl quaternary ammonium salts,alkyl dimethyl benzyl quaternary ammonium salts, dialkyl dimethylquaternary ammonium salts, and imidazolinium salts. Nonionic surfactantsinclude alcohol alkoxylates, alkylphenol alkoxylates, block copolymersof ethylene, propylene and butylene oxides, alkyl dimethyl amine oxides,alkyl-bis(2-hydroxyethyl)amine oxides, alkyl amidopropyl dimethyl amineoxides, alkylamidopropyl-bis(2-hydroxyethyl)amine oxides, alkylpolyglucosides, polyalkoxylated glycerides, sorbitan esters andpolyalkoxylated sorbitan esters, and alkoyl polyethylene glycol estersand diesters. Also included are betaines and sultanes, amphotericsurfactants such as alkyl amphoacetates and amphodiacetates, alkylamphopropripionates and amphodipropionates, and alkyliminodiproprionate.

The surfactant can be a quaternary ammonium compound, an amine oxide, anionic or nonionic surfactant, or any combination thereof. Suitablequaternary amine compounds include, but are not limited to, alkyl benzylammonium chloride, benzyl cocoalkyl(C₁₂-C₁₈)dimethylammonium chloride,dicocoalkyl (C₁₂-C₁₈)dimethylammonium chloride, ditallowdimethylammonium chloride, di(hydrogenated tallow alkyl)dimethylquaternary ammonium methyl chloride, methyl bis(2-hydroxyethylcocoalkyl(C₁₂-C₁₈) quaternary ammonium chloride, dimethyl(2-ethyl)tallow ammonium methyl sulfate, n-dodecylbenzyldimethylammoniumchloride, n-octadecylbenzyldimethyl ammonium chloride,n-dodecyltrimethylammonium sulfate, soya alkyltrimethylammoniumchloride, and hydrogenated tallow alkyl (2-ethylhyexyl)dimethylquaternary ammonium methyl sulfate.

(q) Additional Components

Compositions made according to the invention can further includeadditional functional agents or additives that provide a beneficialproperty. The amount of an additional agent or additive, when present,will vary according to the particular composition being manufactured andits intended use as one skilled in the art will appreciate.

3. METHODS OF PREPARING THE COMPOSITIONS

Compositions of the invention can be prepared by combining a polyaminecomponent and a sulfonic acid component to provide a polyamine sulfonicacid salt. To the polyamine sulfonic acid salt can be added one or moreadditional corrosion inhibitors, synergists, and/or solvents.

4. METHODS OF USE

The compositions of the invention can be used for inhibiting corrosionand/or removing hydrocarbonaceous deposits (e.g., schmoo) in oil and gasapplications. The compositions can be used for inhibiting corrosionand/or removing hydrocarbonaceous deposits by treating a gas or liquidstream with an effective amount of a composition of the invention, asdescribed herein. The compositions of the invention can be used in anyindustry where it is desirable to inhibit corrosion and/or removehydrocarbonaceous deposits from a surface.

The cleaner/corrosion inhibitor compositions can be used in watersystems, condensate/oil systems/gas systems, or any combination thereof.The compositions can be applied to a gas or liquid produced, or used inthe production, transportation, storage, and/or separation of crude oilor natural gas. The compositions can be applied to a gas stream used orproduced in a coal-fired process, such as a coal-fired power plant. Thecompositions can be applied to a gas or liquid produced or used in awaste-water process, a farm, a slaughter house, a land-fill, amunicipality waste-water plant, a coking coal process, or a biofuelprocess.

A fluid to which the compounds and compositions can be introduced can bean aqueous medium. The aqueous medium can comprise water, gas, andoptionally liquid hydrocarbon. A fluid to which the compounds andcompositions can be introduced can be a liquid hydrocarbon. The liquidhydrocarbon can be any type of liquid hydrocarbon including, but notlimited to, crude oil, heavy oil, processed residual oil, bituminousoil, coker oils, coker gas oils, fluid catalytic cracker feeds, gas oil,naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jetfuel, gasoline, and kerosene. The fluid or gas can be a refinedhydrocarbon product.

A fluid or gas treated with a composition of the invention can be at anyselected temperature, such as ambient temperature or an elevatedtemperature. The fluid (e.g., liquid hydrocarbon) or gas can be at atemperature of from about 40° C. to about 250° C. The fluid or gas canbe at a temperature of from −50° C. to 300° C., 0° C. to 200° C., 10° C.to 100° C., or 20° C. to 90° C. The fluid or gas can be at a temperatureof −50° C., −45° C., −40° C., −35° C., −30° C., −25° C., −20° C., −15°C., −10° C., −5° C., or 0° C. The fluid or gas can be found in an arcticenvironment, and can have a temperature and salinity typical of suchenvironment.

The compositions of the invention can be added to a fluid at variouslevels of water cut. For example, the water cut can be from 0% to 100%volume/volume (v/v), from 1% to 80% v/v, or from 1% to 60% v/v. Thefluid can be an aqueous medium that contains various levels of salinity.The fluid can have a salinity of 0% to 25%, about 1% to 24%, or about10% to 25% weight/weight (w/w) total dissolved solids (TDS).

The fluid or gas in which the compositions of the invention areintroduced can be contained in and/or exposed to many different types ofapparatuses. For example, the fluid or gas can be contained in anapparatus that transports fluid or gas from one point to another, suchas an oil and/or gas pipeline. The apparatus can be part of an oiland/or gas refinery, such as a pipeline, a separation vessel, adehydration unit, or a gas line. The compositions can be introduced tolarge diameter flow lines of from about 1 inch to about 4 feet indiameter, small gathering lines, small flow lines and headers. The fluidcan be contained in and/or exposed to an apparatus used in oilextraction and/or production, such as a wellhead. The apparatus can bepart of a coal-fired power plant. The apparatus can be a scrubber (e.g.,a wet flue gas desulfurizer, a spray dry absorber, a dry sorbentinjector, a spray tower, a contact or bubble tower, or the like). Theapparatus can be a cargo vessel, a storage vessel, a holding tank, or apipeline connecting the tanks, vessels, or processing units. The fluidor gas can be contained in water systems, condensate/oil systems/gassystems, or any combination thereof.

The compositions of the invention can be introduced into a fluid or gasby any appropriate method for ensuring dispersal through the fluid orgas. The inhibitor composition can be added at a point in a flow lineupstream from the point at which corrosion prevention and/or schmooremoval is desired. The compositions can be injected using mechanicalequipment such as chemical injection pumps, piping tees, injectionfittings, atomizers, quills, and the like. The compositions of theinvention can be introduced with or without one or more additional polaror non-polar solvents depending upon the application and requirements.

The compositions of the invention can be pumped into an oil and/or gaspipeline using an umbilical line. A capillary injection systems can beused to deliver the compositions to a selected fluid. The compositionscan be introduced into a liquid and mixed. The compositions can beinjected into a gas stream as an aqueous or non-aqueous solution,mixture, or slurry. The fluid or gas can be passed through an absorptiontower comprising a composition of the invention.

The compositions can be applied to a fluid or gas to provide anyselected concentration. In practice, the compositions of the inventionare typically added to a flow line to provide an effective treating doseof the described compositions from about 0.01 to about 5,000 ppm. Thecompositions can be applied to a fluid or gas to provide at aconcentration of about 1 parts per million (ppm) to about 1,000,000 ppm,about 1 parts per million (ppm) to about 100,000 ppm, or about 10 ppm toabout 75,000 ppm. The compositions can be applied to a fluid at aconcentration of about 100 ppm to about 10,000 ppm, about 200 ppm toabout 8,000 ppm, or about 500 ppm to about 6,000 ppm. The compositionscan be applied to a fluid or gas to provide a concentration of 10 ppm,20 ppm, 100 ppm, 200 ppm, 500 ppm, or 1,000 ppm. Each system can haveits own requirements, and the effective amount of a composition tosufficiently reduce the rate of corrosion and/or remove schmoo can varywith the system in which it is used.

The compositions can be applied continuously, in batch, or a combinationthereof. For example, the composition doses can be continuous to preventcorrosion or intermittent (i.e., batch treatment) to removehydrocarbonaceous deposits. The composition doses can becontinuous/maintained and/or intermittent to both inhibit corrosion andremove deposits. Dosage rates for continuous treatments typically rangefrom about 10 to about 500 ppm, or about 10 to about 200 ppm. Dosagerates for batch treatments typically range from about 10 to about400,000 ppm, or about 10 to about 20,000 ppm. The composition can alsobe applied as a pill to a pipeline, providing a high dose (e.g., 20,000ppm) of the composition.

The flow rate of a flow line in which the composition is used can bebetween 0 and 100 feet per second, or between 0.1 and 50 feet persecond. The compositions can be formulated with water in order tofacilitate addition to the flow line.

The compositions, methods, and processes of the invention will be betterunderstood by reference to the following examples, which are intended asan illustration of and not a limitation upon the scope of the invention.

5. EXAMPLES

The foregoing can be better understood by reference to the followingexamples, which are presented for purposes of illustration and are notintended to limit the scope of the invention.

Example 1 Cleaner/Corrosion Inhibitor Composition

Table 1 summarizes an exemplary composition of the invention (“Example1”). The composition includes 35 wt. % of a polyamine sulfonic acid saltcomponent formed from 20 wt. % of a polyamine component (EthyleneamineE-100; Huntsman Corporation) and 15 wt. % of a sulfonic acid component(dodecylbenzenesulfonic acid), based on total weight of the composition.The composition further includes a synergist and a solvent. Thesynergist is 2-mercaptoethanol and is present in an amount of 8 wt. %based on total weight of the composition. The solvent is methanol and ispresent in an amount of 57 wt. % based on total weight of thecomposition.

The composition of Table 1 was prepared by combining Ethylene E-100 withdodecylbenzenesulfonic acid to provide a polyaminedodecylbenzenesulfonic acid salt. To the salt was added2-mercaptoethanol and methanol.

TABLE 1 Composition of Example 1 Amount Ex.1 Component (wt %) (wt %)Polyamine Ethyleneamine E-100 100 20 Sulfonic Acid Lineardodecylbenzenesulfonic acid 100 15 Synergist 2-mercaptoethanol 100 8Solvent methanol 100 57

Example 2 Cleaner/Corrosion Inhibitor Composition

Table 2 summarizes another exemplary composition of the invention(“Example 2”). The composition includes 35 wt. % of a polyamine sulfonicacid salt component formed from 20 wt. % of a polyamine component(Ethyleneamine E-100; Huntsman Corporation) and 15 wt. % of a sulfonicacid component (dodecylbenzenesulfonic acid), based on total weight ofthe composition. The composition further includes a corrosion inhibitor,a synergist, and a solvent. The corrosion inhibitor is present in anamount of 15 wt. % based on total weight of the composition, andconsists of an imidazolinium salt, a pyridinium salt, and an ethoxylatedalkyl amine. The synergist is 2-mercaptoethanol and is present in anamount of 8 wt. % based on total weight of the composition. The solventis methanol and is present in an amount of 42 wt. % based on totalweight of the composition.

The composition of Table 2 was prepared by combining Ethylene E-100 withdodecylbenzenesulfonic acid to provide a polyaminedodecylbenzenesulfonic acid salt. To the salt was added the corrosioninhibitor, followed by 2-mercaptoethanol, and methanol.

TABLE 2 Composition of Example 2 Amount Ex.2 Component (wt %) (wt %)Polyamine Ethyleneamine E-100 100 20 Sulfonic Acid lineardodecylbenzenesulfonic acid 100 15 Corrosion Inhibitor imidazoliniumsalt 10-50 15 pyridinium salt 10-50 ethoxylated alkyl amine 10-50Synergist 2-mercaptoethanol 100 8 Solvent methanol 100 42

Example 3 Corrosion Performance Evaluation Via Bubble Test

The compositions of Examples 1 and 2 were evaluated for corrosionperformance via a bubble test procedure. The bubble test simulates lowflow areas where little or no mixing of water and oil occurs. The testwas conducted using synthetic brine and field crude oil. The ratio ofwater to oil was 90:10. The brine was placed into kettles and purgedwith carbon dioxide. The brine was continually purged with carbondioxide to saturate the brine prior to starting the test. After the testbegan, the test cell was blanketed with carbon dioxide through theduration of the test to maintain saturation. The kettles were stirred at150 revolutions per minute (rpm) for the duration of the test tomaintain thermal equilibrium at 60° C. The corrosion rate was measuredby Linear Polarization Resistance (LPR) techniques. The workingelectrode used was 1018 carbon steel. The counter and referenceelectrodes were both 316 stainless steel. The electrodes were allcleaned and polished prior to testing. The kettles were dosed with thesamples and a blank as described in Table 3. The results of the bubbletest are shown in Table 3, as well as FIG. 1.

TABLE 3 Bubble test results Dosage 12 hrs after dosing 18 hrs afterdosing End of testing Chemical (ppm) mpy mmpy % P mpy mmpy % P mpy mmpy% P Blank 0 89.0 2.26 N/A 88.8 2.26 N/A 89.8 2.3 N/A Incumbent 1^(a) 201.5 0.04 98.3 1.51 0.04 98.3 1.45 0.04 98.4 Incumbent 2^(b) 20 4.1 0.1095.4 5.60 0.14 93.7 5.30 0.13 94.1 Example 1^(c) 20 0.9 0.02 98.5 1.00.02 98.3 0.86 0.02 98.5 Example 2^(d) 20 1.3 0.03 98.6 1.7 0.04 98.11.66 0.04 98.2 ppm = parts per million; mpy = Mils per year, mmpy =millimeters per year; % P = percent protection ^(a)Commerciallyavailable corrosion inhibitor comprising a blend of quaternary ammoniumcompounds, an imidazoline, and 2-mercaptoethanol; ^(b)Commerciallyavailable corrosion inhibitor comprising a blend of quaternary ammoniumcompounds, an imidazoline and 2-mercaptoethanol. ^(c)Composition ofExample 1; ^(d)Composition of Example 2.

Prior to dosage, the baseline corrosion rate was established in eachkettle. Each sample was then added to the respective kettle and LPRmeasurements taken at 12, 18, and 20 hours later (end of testing). Theuntreated (blank) kettle showed very little change in corrosion rateduring the test with a starting and ending corrosion rate of 89.0 and89.8 mpy, respectively. All kettles that received chemical(s)demonstrated a reduction in corrosion compared to the baseline corrosionrate. Examples 1 and 2 showed equal or superior corrosion protection(>98%) compared to the incumbent commercial corrosion inhibitor/cleanerproducts when dosed at 20 ppm.

Example 4 Cleaning Performance Evaluation Via Flow Test

The composition of Example 2 was evaluated for cleaning performance. Aflow test, known as a Dynamic Schmoo Removal Loop (“DSRL”), was set upto evaluate the efficacy of the composition at removinghydrocarbonaceous deposits from a pipeline steel surface under low flowconditions. Tests were conducted at 50, 100, 200, 500, and 1,000 ppm ofcomposition in brine at 122° F.

The brine flowed through an acrylic-walled cell having internaldimensions of 20 mm side length and 40 mm height and having an inlet andoutlet connection of about 3 mm internal diameter and 10 mm from thebase on opposite sides of the cell. Brine flow through the cell wascontrolled with a peristaltic pump set at 1-liter every three minutes. Abrine reservoir of about 400 mL was kept at 122° F., and the cell wasplaced on a stage and also held at 122° F.

A freshly polished 1018 mild steel coupon was placed in the empty cellwith a known mass of schmoo (from an Alaskan pipeline source) applied tothe coupon. The cell was filled with brine and circulation commenced forone hour. The coupon was then removed from the cell and air-dried andweighed. The coupons were also weighed after removing the remainingschmoo to normalize for coupon corrosion losses.

Table 4 and FIG. 2 summarize the DSRL performance data. The compositionof Example 2 unexpectedly showed 61% removal of mass from the testsamples, whereas Incumbent 1 demonstrated 35% removal. Without beingbound by theory, it is believed the unexpected superior cleaningperformance can be a result of synergy of the dodecylbenzenesulfonicacid and polyamine to provide a polyamine salt composition (a cleaner)with reduced charge repulsion at treated surfaces (e.g., pipelines).

TABLE 4 Mass Removal Results Dosage % Schmoo Removal (ppm) Example 2Incumbent 1 Incumbent 2 0 6 5 5 50 8 100 13 5 5 200 21 20 16 500 49 3523 1000 61 35 38

Any ranges given either in absolute terms or in approximate terms areintended to encompass both, and any definitions used herein are intendedto be clarifying and not limiting. Notwithstanding that the numericalranges and parameters setting forth the broad scope of the invention areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.Moreover, all ranges disclosed herein are to be understood to encompassany and all subranges (including all fractional and whole values)subsumed therein.

Furthermore, the invention encompasses any and all possible combinationsof some or all of the various embodiments described herein. Any and allpatents, patent applications, scientific papers, and other referencescited in this application, as well as any references cited therein, arehereby incorporated by reference in their entirety.

What is claimed is:
 1. A composition for inhibiting corrosion and/orremoving hydrocarbonaceous deposits in oil and gas applications, thecomposition comprising a polyamine sulfonic acid salt component and asynergist selected from the group consisting of thioglycolic acid,3,3′-dithiodipropionic acid, thiosulfate, thiourea, 2-mercaptoethanol,L-cysteine, tert-butyl mercaptan, and combinations thereof.
 2. Thecomposition of claim 1 wherein the polyamine sulfonic acid saltcomponent is formed by reaction of a polyamine component with a sulfonicacid component.
 3. The composition of claim 2, wherein the polyaminecomponent comprises a polyalkylene polyamine, wherein the polyalkylenepolyamine comprises a polyethylene polyamine, a polypropylene polyamine,a polybutylene polyamine, or a combination thereof.
 4. The compositionof claim 3, wherein the polyamine component comprises a mixture oftetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andhexaethyleneheptamine (HEHA).
 5. The composition of claim 2, wherein thesulfonic acid component is selected from the group consisting of an arylsulfonic acid, an alkyl sulfonic acid, an arylalkyl sulfonic acid, and acombination thereof.
 6. The composition of claim 1, wherein thepolyamine sulfonic acid salt component comprises a salt selected fromthe group consisting of: a tetraethylenepentamine dodecylbenzenesulfonicacid salt; a pentaethylenehexamine dodecylbenzenesulfonic acid salt; ahexaethyleneheptamine dodecylbenzenesulfonic acid salt; and acombination thereof.
 7. The composition of claim 1, further comprising acorrosion inhibitor component.
 8. The composition of claim 7, whereinthe corrosion inhibitor component comprises an imidazoline of Formula(I) or an imidazolinium salt of Formula (II):

wherein R¹⁰ is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R¹² and R¹³are independently a C₁-C₆ alkyl group or hydrogen, R¹¹ and R¹⁴ areindependently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆arylalkyl; and X⁻ is halide, chloride, bromide, iodide, carbonate,sulfonate, phosphate, or an anion of an organic carboxylic acid; or atautomer thereof.
 9. The composition of claim 8, wherein R¹⁰ is an alkylmixture typical in tall oil fatty acid (TOFA), R¹¹ is benzyl, R¹² andR¹³ are each hydrogen, R¹⁴ is hydroxyethyl, and X⁻ is chloride.
 10. Thecomposition of claim 7, wherein the corrosion inhibitor componentcomprises a compound of Formula (III):

wherein R⁹ is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atom; and X⁻ ischloride, bromide, or iodide.
 11. The composition of claim 10, whereinR⁹ is benzyl, and X⁻ is chloride.
 12. The composition of claim 7,wherein the corrosion inhibitor component comprises an ethoxylatedamine.
 13. The composition of claim 12, wherein the ethoxylated amine isethoxylated tallow amine.
 14. A method of inhibiting corrosion at asurface and/or removing hydrocarbonaceous deposits from a surface, themethod comprising adding a composition to a fluid which contacts asurface of a wellbore or equipment used in production, processing,transportation, storage or separation of the fluid to inhibit corrosionand/or remove hydrocarbonaceous deposits from the surface, thecomposition comprising a polyamine sulfonic acid salt component, and thefluid comprising natural gas or a liquid hydrocarbon.
 15. The method ofclaim 14, wherein an effective amount of the composition is provided atthe surface when the composition provides greater than or equal to 40%schmoo removal in a Dynamic Schmoo Removal Loop (“DSRL”) test conductedat a dosage of 500 or 1,000 ppm of the composition in brine at 122° F.16. The composition of claim 1 wherein the polyamine sulfonic acid saltcomponent comprises at least one salt selected from atetraethylenepentamine dodecylbenzenesulfonic acid salt, apentaethylenehexamine dodecylbenzenesulfonic acid salt, and ahexaethyleneheptamine dodecylbenzenesulfonic acid salt; the synergistcomprises 2-mercaptoethanol; and the composition further comprisesmethanol; and optionally comprises a corrosion inhibitor componentcomprising an imidazolinium salt, a pyridinium salt, and an ethoxylatedalkyl amine.
 17. The composition of claim 16, wherein the polyaminesulfonic acid salt component comprises a mixture of atetraethylenepentamine dodecylbenzenesulfonic acid salt, apentaethylenehexamine dodecylbenzenesulfonic acid salt, and ahexaethyleneheptamine dodecylbenzenesulfonic acid salt.
 18. Thecomposition of claim 16, wherein the polyamine sulfonic acid saltcomponent is present in an amount of 10-70 wt. %, the corrosioninhibitor component is present in an amount of 5-50 wt. %,2-mercaptoethanol is present in an amount of 1-20 wt. %, and methanol ispresent in an amount of 10-80 wt. %, based on the total weight of thecomposition.
 19. The method of claim 14, wherein an effective amount ofthe composition is provided at the surface when the composition providesat least 95% protection after 12 hours for a 1018 carbon steel workingelectrode in a bubble test, wherein the bubble test is characterized by:(a) a testing temperature of about 60° C.; (b) a carbon dioxidesaturated liquid medium of 10% field crude oil and 90% synthetic brine;and (c) an inhibitor dosage of 20 ppm of the composition based on totalfluids.
 20. The method of claim 14 wherein the equipment comprises apipeline, a storage vessel, downhole injection tubing, a flow line, oran injection line.
 21. The method of claim 14 wherein the liquidhydrocarbon comprises crude oil, heavy oil, processed residual oil,bituminous oil, coker oil, gas oil, fluid catalytic cracker feed orslurry, naphtha, diesel fuel, fuel oil, jet fuel, gasoline, or kerosene.22. The method of claim 14 wherein the polyamine sulfonic acid saltcomponent comprises a salt selected from the group consisting of: atetraethylenepentamine dodecylbenzenesulfonic acid salt; apentaethylenehexamine dodecylbenzenesulfonic acid salt; ahexaethyleneheptamine dodecylbenzenesulfonic acid salt; and acombination thereof; and/or the composition further comprises acorrosion inhibitor comprising: (A) an imidazoline of Formula (I) or animidazolinium salt of Formula (II):

wherein R¹⁰ is a C₁-C₂₀ alkyl or a C₁-C₂₀ alkoxyalkyl group; R¹² and R¹³are independently a C₁-C₆ alkyl group or hydrogen, R¹¹ and R¹⁴ areindependently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl, or C₁-C₆arylalkyl; and X⁻ is halide, chloride, bromide, iodide, carbonate,sulfonate, phosphate, or an anion of an organic carboxylic acid; or atautomer thereof; (B) a compound of Formula (III):

wherein R⁹ is an alkyl group, an aryl group, or an arylalkyl group,wherein said alkyl groups have from 1 to about 18 carbon atom; and X⁻ ischloride, bromide, or iodide; or (C) an ethoxylated amine.